Characterizing a nonclassical carbene with coupled cluster methods: cyclobutylidene. Issue 35 (19th August 2016)

• Record Type: Journal Article
• Authors: Wang, Xiao; Agarwal, Jay; Schaefer III, Henry F.
• Is Part Of: Physical chemistry chemical physics. Volume 18:Issue 35(2016)
• Page Start: 24560
• Page End: 24568
• Publication Date: 2016-08-19
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c6cp03513b
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Cyclobutylidene is a nonclassical compound that undergoes rapid rearrangement. Three reaction paths on the lowest potential energy surface are examined with theory; reaction barriers and kinetic rates are reported, among other analyses. Abstract : Carbenes represent a special class of reactive compounds that possess a lone pair of electrons on a carbon atom. Among the myriad examples of carbenes in the literature, cyclobutylidene stands out as a unique nonclassical compound that includes transannular interaction between opposing C1 and C3 carbon atoms within a four-membered ring. On its lowest potential energy surface (X̃ 1 A′), cyclobutylidene quickly rearranges, following three reaction paths: (i) 1, 2-H migration; (ii) 1, 2-C migration; and, (iii) 1, 3-H migration. Herein, this reactivity is examined with high-level coupled-cluster methods [up to CCSDT(Q)]. At this level of theory, combined with extrapolation techniques to obtain energies at the complete basis set (CBS) limit, the long-standing disparity between theoretical and experimental results is resolved. Specifically, cyclobutylidene is predicted to prefer 1, 2-C migration rather than 1, 2-H migration. Rate constants for the three reaction paths are obtained from canonical variational transition state theory (CVT) and yield reasonable agreement with existing experimental results. Further characterization of cyclobutylidene is also reported: the singlet–triplet gap (Δ E S–T ) is found to be −9.3 kcal mol −1 at the CCSDT(Q)/CBS level of theory, and anharmonic vibrational frequencies are determined with second-order vibrational perturbation theory (VPT2).